Ethanol → 1-Ethyl (3E)-2-amino-4-methyl-5-phosphono-3-pentenoate

HRID 1682313Notes

Reaction equation

HRID 1682313 reaction equation
C[Si](C)(C)Br.[CH2:6]([O:8][C:9](=[O:28])[CH:10]([NH:25]C=O)/[CH:11]=[C:12](\[CH3:24])/[CH2:13][P:14]([O:20]C(C)C)([O:16]C(C)C)=[O:15])[CH3:7].C(O)C>ClCCl>[CH2:6]([O:8][C:9](=[O:28])[CH:10]([NH2:25])/[CH:11]=[C:12](\[CH3:24])/[CH2:13][P:14]([OH:16])([OH:20])=[O:15])[CH3:7]

Participants

5

Reactant 3

HCID 702EthanolHCID 76113BromotrimethylsilaneHCID 86745094HCID 86745094, compound

Product 1

HCID 63723341-Ethyl (3E)-2-amino-4-methyl-5-phosphono-3-pentenoate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

56.7 ml of trimethylbromosilane are added dropwise within a period of 15 minutes at 20° to a solution of 25.42 g of E-2-formylamino-4-methyl-5-diisopropylphosphono-3-pentenoic acid ethyl ester in 102 ml of dry dichloromethane. After stirring at room temperature for 20 hours, 102 ml of ethanol are added dropwise within a period of 15 minutes, and the whole is stirred for a further 20 hours. The clear reaction solution is then completely concentrated by evaporation in vacuo. The residue is concentrated by evaporation a further three times in each case after the addition of 100 ml of toluene. The oily residue is dissolved in 102 ml of ethanol, and a solution of 102 ml of propylene oxide in 102 ml of ethanol is added dropwise thereto. The product, obtained in crystalline form, is filtered off after 2 hours (room temperature) and washed with ethanol and ether. After drying (80°, 4 hours) under a high vacuum, E-2-amino-4-methyl-5 -phosphono-3-pentenoic acid ethyl ester is obtained in analytically pure form, m.p. 212° (decomp.).

Workup

  1. stirringthe whole is stirred for a further 20 hours
  2. concentrationThe clear reaction solution is then completely concentrated by evaporation in vacuo
  3. concentrationThe residue is concentrated by evaporation a further three times in each case
  4. additionafter the addition of 100 ml of toluene
  5. dissolutionThe oily residue is dissolved in 102 ml of ethanol
  6. additiona solution of 102 ml of propylene oxide in 102 ml of ethanol is added dropwise
  7. customThe product, obtained in crystalline form
  8. filtrationis filtered off after 2 hours (room temperature)
  9. washwashed with ethanol and ether
  10. customAfter drying (80°, 4 hours) under a high vacuum

Sources & evidence

ORD record
ord-11d32d8fbdf8473d96f019a66c4f9ec6
Source dataset
uspto-grants-1992_12
Patent number
US05175344

Reaction notes

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